CN114160801B - Equipment and method for preparing alloy nano particles by arc method - Google Patents
Equipment and method for preparing alloy nano particles by arc method Download PDFInfo
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- CN114160801B CN114160801B CN202111280216.4A CN202111280216A CN114160801B CN 114160801 B CN114160801 B CN 114160801B CN 202111280216 A CN202111280216 A CN 202111280216A CN 114160801 B CN114160801 B CN 114160801B
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- 239000000956 alloy Substances 0.000 title claims abstract description 78
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 70
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 67
- 238000000034 method Methods 0.000 title claims description 26
- 238000007740 vapor deposition Methods 0.000 claims abstract description 46
- 238000007789 sealing Methods 0.000 claims abstract description 35
- 238000009423 ventilation Methods 0.000 claims abstract description 18
- 239000002245 particle Substances 0.000 claims abstract description 10
- 238000009826 distribution Methods 0.000 claims abstract description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 61
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 43
- 239000010937 tungsten Substances 0.000 claims description 43
- 229910052721 tungsten Inorganic materials 0.000 claims description 43
- 229910052786 argon Inorganic materials 0.000 claims description 32
- 239000007789 gas Substances 0.000 claims description 21
- 238000010438 heat treatment Methods 0.000 claims description 21
- 239000010949 copper Substances 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 238000011049 filling Methods 0.000 claims description 12
- 229910018565 CuAl Inorganic materials 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 229910000838 Al alloy Inorganic materials 0.000 claims description 7
- 238000004140 cleaning Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 6
- 239000006104 solid solution Substances 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- 230000001276 controlling effect Effects 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
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- 238000002844 melting Methods 0.000 claims description 3
- 230000008018 melting Effects 0.000 claims description 3
- 238000002161 passivation Methods 0.000 claims description 3
- 238000004064 recycling Methods 0.000 claims description 3
- 229920006395 saturated elastomer Polymers 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000000843 powder Substances 0.000 abstract description 6
- 238000000151 deposition Methods 0.000 description 4
- 238000011065 in-situ storage Methods 0.000 description 4
- 230000008021 deposition Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000010891 electric arc Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011858 nanopowder Substances 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- 229910002065 alloy metal Inorganic materials 0.000 description 1
- 238000012984 biological imaging Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
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- 238000000605 extraction Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
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- 229910052751 metal Inorganic materials 0.000 description 1
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/14—Making metallic powder or suspensions thereof using physical processes using electric discharge
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/12—Making metallic powder or suspensions thereof using physical processes starting from gaseous material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
Abstract
The upper part of the equipment is a vapor deposition chamber which is connected with a sealing chamber, the outer wall of the vapor deposition chamber is provided with a heater, the vapor deposition chamber is connected with a water-cooled anode and a water-cooled ventilation cathode, and the lower part of the vapor deposition chamber is inserted into a trapping chamber through a conical trapping tank. The vapor deposition chamber is connected with a molecular pump and a mechanical pump through valves, and the mechanical pump, the molecular pump and the heater are all connected with a power supply and a control cabinet. Alloy nano particles can be continuously prepared in large quantity; the arc shape is controllable, the particle size distribution of the powder is narrow, and the content of the generated alloy nano particles is controllable; the alloy nano-particles have novel structure, simple and effective operation; different elements can be prepared into alloy nano particles according to theory.
Description
Technical Field
The invention belongs to the technical field of new material preparation, and relates to equipment and a method for preparing alloy nano particles by an arc method.
Background
The advent of alloy nanoparticles will greatly expand the research and application range of the nanomaterial field. Theoretically, the controlled integration of a variety of elements with distinct properties into nanoparticles would bring about more variation and possibility of the properties of the nanoparticles. Controlling the preparation of nanoparticles at the nanoscale from a variety of incompatible elements is a significant challenge. By adjusting parameters such as arc current, voltage, atomic collision frequency, direction of movement, and ambient temperature, the chemical composition, size, and phase composition (solid solution or phase separation) of the nanoparticles can be well controlled. The existing equipment is difficult to adjust and control the parameters, alloy nano powder cannot be continuously prepared for a long time, and the working efficiency is low.
Disclosure of Invention
Object of the Invention
Aiming at the problems that the existing equipment is difficult to realize adjustment and control of the parameters, alloy nano powder cannot be continuously prepared for a long time, the alloy powder content is low, and the working efficiency is low, the invention provides equipment and a method for preparing alloy nano particles by an electric arc method.
Technical proposal
An arc method for preparing nano-particles of alloy features that the controllable high-temp region is increased at the edge of arc and the high-smelting-point tungsten sheet is put in the evaporated alloy. The upper part of the equipment is a vapor deposition chamber which is connected with a sealing chamber, a heater with variable length and controllable temperature is arranged in the vapor deposition chamber, the vapor deposition chamber is connected with a water-cooled anode and a water-cooled ventilation cathode, and the lower part of the vapor deposition chamber is inserted into a trapping chamber through a conical trapping tank.
The vapor deposition chamber is connected with a molecular pump and a mechanical pump through valves, and the mechanical pump, the molecular pump and the heater are all connected with a power supply and a control cabinet.
The central passage is arranged in the middle of the longitudinal direction of the heater, the heating part is arranged around the central passage, the middle part of the heater is provided with a telescopic structure, the bottom of the heater is provided with a heat-blocking tungsten plate, and the heater is connected with a heating power supply.
One end of the sealing chamber is provided with a heat shielding plate, the sealing chamber is connected with the vapor deposition chamber through the deposition chamber wall, the sealing chamber is internally provided with gloves, tools and raw materials, the other end of the sealing chamber is provided with a flange, the sealing chamber is led out from inside to outside and passes through gas paths communicated with two sides of the gloves, and the gas paths communicated with two sides of the gloves pass through a gas path flange switch.
The axial inside of the cathode is provided with a water passage, the axial outside of the cathode is provided with a gas passage, and the head of the cathode is provided with a copper nut for fixing a cathode head tungsten rod.
The method for preparing the alloy nano-particles by the arc method comprises the following steps:
(1) cutting alloy cake (such as CuAl) to be evaporated into two pieces in the middle vertical height direction, placing proper tungsten sheet in the middle to make sandwich type, placing on water-cooled anode, and using tungsten rod of water-cooled ventilation cathode as cathode head; turning on circulating water and power supply, and vacuumizing the vapor deposition chamber and the sealing chamber to 2×10 by using mechanical pump and molecular pump unit -1 Pa. Filling argon into the vapor deposition chamber and the sealing chamber, cleaning for 2-3 times, and vacuumizing to 2×10 -3 An environment of Pa;
the diameter phi of the CuAl cake to be evaporated is 39-41mm, the height is 14-16mm, the diameter phi of the tungsten plate is 2-5mm, the height is 1-2mm, the diameter phi of the tungsten rod is 4-6mm, and the length is 115-125mm; the purity of the argon used is 99.99%; the purity of the hydrogen is 99.99%.
(2) Filling argon and hydrogen mixed gas with pressure ratio of P Ar :P H2 ＝5:1～1:1；
(3) Starting a switch of a controllable Wen Zhuzhuang heater, adjusting the temperature to 20-1200 ℃, starting a water pump and an air pump valve of a control cabinet, adjusting the ventilation volume of a water-cooling ventilation cathode to 20-40 sccm, and enabling air flow to be used for protecting a cathode head tungsten rod and controlling an arc;
(4) turning on an arc power supply, starting an arc with small current, and stabilizing the arc after starting the arc, wherein the arc current is 150-200A, the voltage is 30-35V, and the arc striking time is 1-4 h;
(5) after stopping the arc, using 1-2X 10 4 Pa air and 9 to 8 multiplied by 10 4 The mixed gas of Pa argon is circularly passivated for 1 to 3 hours, and is pumped to 5 multiplied by 10 after stopping for 1 hour 4 Pa, according to the air argon ratio 1:5 to 1:3 aerating, and recycling passivation for 1-3 h to prepare Cu 3 Al alloy nanoparticles, wherein the alloy nanoparticle component is related to the starting alloy block component, the quantity of tungsten flakes put in the alloy material, the melting point of each element, the saturated vapor pressure, the heating temperature and the atmosphere. Prepared Cu 3 The Al nano-particle component is a single solid solution, the particle component and the content are related to the starting alloy block component, the quantity of tungsten flakes put into the alloy material, the heating temperature, the atmosphere and the like, Cu 3 The diameter distribution of the Al nano particles is 40-90 nm, and the average particle diameter is 69nm.
The advantages and effects:
the equipment has novel structure, simple and effective operation, in-situ packaging, controllable cooling water temperature, and controllable temperature of atoms passing through a controllable region of 20-1200 ℃ to prepare the designed alloy nano particles, the movement direction of the alloy nano particles is controllable, the content of the alloy nano particles in the powder is high, and the alloy nano particles can be continuously prepared for a long time.
(1) Alloy nano particles can be continuously prepared in large quantity; (2) The arc shape is controllable, the particle size distribution of the powder is narrow, and the content of the generated alloy nano particles is controllable; (3) The alloy nano-particles have novel structure, simple and effective operation; (4) different elements can be prepared, such as: transition metal-transition metal, transition metal-rare earth, rare earth-rare earth alloy nanoparticles.
The alloy nano particles are expected to find application in catalysis, energy storage, biological imaging, plasma imaging and other aspects, and are suitable for popularization and application in the field of preparing other alloy nano particles.
Drawings
FIG. 1 is a schematic view of the apparatus of the present invention;
FIG. 2 is a schematic diagram of a length-scalable controllable Wen Zhuzhuang heater according to the present invention;
FIG. 3 is a side view of the sidewall seal chamber of the present invention;
FIG. 4 is a schematic view of a water cooled vented cathode of the present invention;
FIG. 5 (a) shows Cu prepared according to the present invention 3 TEM image of Al nanoparticles;
FIG. 5 (b) shows Cu prepared according to the present invention 3 XRD pattern of Al nanoparticles.
Reference numerals: 1. a power supply; 2. a control cabinet; 3. a mechanical pump; 4. a molecular pump; 5. a valve; 6. a water-cooled anode; 7. a water-cooled vented cathode; 8. a vapor deposition chamber; 9. a sealed chamber; 10. a heater; 11. a trapping chamber; 12. a heating power supply; 13. a trapping tank; 14. a heater telescoping sleeve; 15. a central passage; 16. a heating part; 17. a heat shielding tungsten plate; 18. a deposition chamber wall; 19. a heat shielding plate; 20. gloves, tools and raw materials; 21. a flange; 22. an air path flange; 23. air paths communicated with two sides of the glove; 24. a cathode head tungsten rod; 25. an air passage; 26. and a water passage.
Detailed Description
The invention is further described with reference to the accompanying drawings:
referring to fig. 1, an apparatus for preparing alloy nanoparticles by an arc process is provided, wherein a vapor deposition chamber 8 is arranged at the upper part of the apparatus, the vapor deposition chamber 8 is connected with a sealing chamber 9, a heater 10 with variable length and controllable temperature is arranged in the vapor deposition chamber 8, the vapor deposition chamber 8 is connected with a water-cooled anode 6 and a water-cooled ventilation cathode 7, and the lower part of the vapor deposition chamber 8 is inserted into a trapping chamber through a conical trapping tank 13.
The vapor deposition chamber 8 is connected with the molecular pump 4 and the mechanical pump 3 through the valve 5, the mechanical pump 3 and the molecular pump 4 are both connected with the power supply 1 and the control cabinet 2, and the heater 10 is connected with the heating power supply 12.
Referring to fig. 2, a central passage 15 is provided in the middle of the longitudinal direction of the heater 10, a heating portion 16 is provided around the central passage 15, a heater telescopic sleeve 14 is provided in the middle of the heater 10, a heat shielding tungsten plate 17 is provided at the bottom of the heater 10, and the heater 10 is connected with a heating power supply 12.
Referring to fig. 3, a heat shielding plate 19 is disposed at one end of the sealing chamber 9, the sealing chamber 9 is connected with the vapor deposition chamber 8 through a deposition chamber wall 18, sealing processing gloves, tools (such as a collecting brush) and raw materials are disposed in the sealing chamber 9, a flange 21 is disposed at the other end of the sealing chamber 9, the sealing chamber 9 is led out from inside to outside through air channels 23 communicated with two sides of the gloves, and the air channels 23 communicated with two sides of the gloves determine on-off through the air channel flange 22.
Referring to fig. 4, a water passage 26 is provided in the cathode 7, a gas passage 25 is provided in the cathode 7, and a copper nut is provided at the head of the cathode 7 to fix the cathode head tungsten rod 24.
A freely movable water-cooled ventilation cathode 7 is arranged on the side wall of the vapor deposition chamber 8, a movable multi-shape combined water-cooled anode 6 (such as a crucible-type water-cooled anode with a diameter of 130mm and a copper column shape with adjustable position) is arranged below the vapor deposition chamber 8, the positions of the cathode and the anode corresponding to each other are adjustable, a columnar heater 10 with a telescopic length and controllable temperature (temperatureAdjustable at 20-1200 deg.c), and with sealing chamber 9 inside the side wall; vacuum pumping is carried out by a mechanical pump 3 and a molecular pump 4, and the vacuum degree reaches 2 multiplied by 10 -3 Pa, the valve 5 blocks the steam extraction system and the vapor deposition chamber 8, the power supply 1 and the control cabinet 2 are utilized to start arcs to prepare various alloy nano particles, the trapping tank 13 is used for trapping the alloy nano particles, and the temperature of the heater 10 is controlled by the heating power supply 12; a sealing chamber 9 is arranged at the side part in the vapor deposition chamber 8, and can continuously feed and provide tungsten electrodes and cleaning tools; the vapor deposition chamber 8 and the trapping chamber 11 are connected through a trapping tank 13 and a flange, powder is trapped and then packaged in situ in the trapping chamber 11, and the sealed trapping tank 13 can be continuously exchanged. Different kinds of alloy nano particles can be prepared at one time, and the danger of opening the vapor deposition chamber is reduced.
The method for preparing the alloy nano-particles by the arc method comprises the following steps:
(1) cutting an alloy cake to be evaporated (such as CuAl) into two blocks in the middle vertical height direction, putting a proper tungsten sheet in the middle, making a sandwich type, and placing the sandwich type on a water-cooled anode 6, wherein a tungsten rod of a water-cooled ventilation cathode 7 is used as a cathode head; the circulating water and the power supply are turned on, and the vapor deposition chamber 8 and the sealing chamber 9 are vacuumized to be 2 multiplied by 10 by using the mechanical pump 3 and the molecular pump 4 unit -1 Pa. Filling argon into the vapor deposition chamber 8 and the sealing chamber 9, cleaning for 2-3 times, and vacuumizing to 2×10 -3 An environment of Pa;
(2) filling argon and hydrogen mixed gas with pressure ratio of P Ar :P H2 ＝5:1～1:1；
(3) Starting a controllable Wen Zhuzhuang heater 10, adjusting the temperature to 20-1200 ℃, starting a water pump and an air pump valve of a control cabinet, adjusting the ventilation quantity of the water-cooling ventilation cathode 7 to 20-40 sccm, and enabling air flow to be used for protecting a cathode head tungsten rod and controlling arc;
(4) opening the arc power supply 1, starting an arc with small current, and after the arc is started and regulated, enabling the arc current to be 150-200A, enabling the voltage to be 30-35V, and enabling the arc striking time to be 1-4 h;
(5) after stopping the arc, using 1-2X 10 4 Pa air and 9 to 8 multiplied by 10 4 The mixed gas of Pa argon is circularly passivated for 1 to 3 hours, and is pumped to 5 multiplied by 10 after stopping for 1 hour 4 Pa, according to the air argon ratio 1:5 to 1:3 aerating, and recycling passivation for 1-3 h to prepare Cu 3 Al alloy nano particles, wherein the alloy nano particle component is related to the initial alloy block component, the number of tungsten sheets placed in the alloy material, the heating temperature, atmosphere and the like.
The diameter phi of the CuAl cake to be evaporated is 39-41mm, the height is 14-16mm, the diameter phi of the tungsten plate is 2-5mm, the height is 1-2mm, the diameter phi of the tungsten rod is 4-6mm, and the length is 115-125mm; the purity of the argon used is 99.99%; the purity of the hydrogen is 99.99%.
Prepared Cu 3 The Al nano-particle component is a single solid solution, the particle component and the content are related to the starting alloy block component, the number of tungsten sheets put into the alloy material, the heating temperature, the atmosphere and the like, cu 3 The diameter distribution of the Al nano particles is 49-90 nm, and the average particle diameter is 69nm.
The working principle of the invention is that in pure argon, helium and mixed gas, high temperature is generated after the arc striking of a cathode and an anode through high-frequency arc striking, alloy metal blocks are evaporated, atomic metal irregularly thermally moves and mutually collides to be condensed into alloy nanoclusters, and the alloy nanoclusters pass through a controllable high temperature region after leaving an arc region to form alloy nanoparticles. These alloy nanoparticles are affected by the operating arc parameters, the operating gas, and the temperature of the path traversed. Naturally depositing four walls and entering the trapping tank 13 through the classifier, stopping the arc. After stopping the arc, passivating by a specified program. The alloy nano-particles on the in-situ trapping wall enter a trapping tank 13 through a classifier, and finally are treated in-situ in a treatment chamber through a sealing chamber 9 and a vapor deposition chamber 8. And detecting the alloy content of the residual materials and the powder.
Referring to FIG. 5, cu prepared according to the present invention 3 TEM (a) and XRD (b) of Al nanoparticles
Example 1:
(1) placing 5 tungsten sheets with phi 3mm and height 1mm in the middle of an alloy block (such as CuAl) cake phi 39mm and height 14mm to be evaporated on a water-cooled anode, and taking a water-cooled and ventilated cathode tungsten rod phi 4mm and length 115mm as cathode heads; the circulating water and the power supply are turned on, and the vapor deposition chamber 8 and the sealing chamber 9 are vacuumized to be 2 multiplied by 10 by using a mechanical pump and a molecular pump unit -1 Pa. Filling argon into the vapor deposition chamber 8 and the sealing chamber 9, cleaning for 2-3 times, and vacuumizing to 2×10 -3 An environment of Pa;
(2) filling hydrogen-argon mixed gas with total pressure of 9.5×10 4 Pa, wherein the pressure ratio of argon to hydrogen is P Ar :P H2 ＝1:1；
(3) Starting a controllable Wen Zhuzhuang heater, adjusting the temperature to 500 ℃, starting a circulating pump, and adjusting the cathode ventilation amount to 20sccm;
(4) turning on an arc power supply, starting an arc with small current, and enabling the arc current to be 150A, the voltage to be 30V and the arc striking time to be 2h after the arc is started and stabilized;
(5) after stopping the arc, use 1X 10 4 Pa air and 9X 10 4 The mixed gas of Pa argon is circularly passivated for 1h, and is pumped to 5 multiplied by 10 after stopping for 1h 4 Pa, according to the air argon ratio 1: 5-cycle inflation 1.013X10 5 Pa, passivating for 2h to prepare Cu 3 The Al alloy nano particles, the alloy nano particle composition and content are related to the initial alloy block composition, the number of tungsten sheets put in the alloy material, the heating temperature, atmosphere and the like.
Example 2
(1) Placing 2 tungsten sheets with phi 4mm and height 1mm in the middle of an alloy cake to be evaporated (such as CuAl) with phi 40mm and height 15mm on a water-cooled anode, and taking a water-cooled and ventilated cathode tungsten rod with phi 5mm and length 120mm as a cathode head; the circulating water and the power supply are turned on, and the vapor deposition chamber 8 and the sealing chamber 9 are vacuumized to be 2 multiplied by 10 by using a mechanical pump and a molecular pump unit -1 Pa. Filling argon into the vapor deposition chamber 8 and the sealing chamber 9, cleaning for 2-3 times, and vacuumizing to 2×10 -3 An environment of Pa;
(2) filling hydrogen-argon mixed gas with total pressure of 9.5×10 4 Pa, wherein the pressure ratio of argon to hydrogen is P Ar :P H2 ＝2:1；
(3) Starting a controllable Wen Zhuzhuang heater, adjusting the temperature to 800 ℃, starting a circulating pump, and adjusting the cathode ventilation amount to 30sccm;
(4) turning on an arc power supply, starting an arc with small current, and enabling the arc current to be 180A, the voltage to be 32V and the arc striking time to be 3h after the arc is started and stabilized;
(5) after stopping the arc, use 1.5×10 4 Pa air and 8.5X10 4 The mixed gas of Pa argon is circularly passivated for 2 hours, and after stopping for 2 hours, the mixed gas is pumped to 5.5X10 4 Pa, according to the air argon ratio 1:4 cycle aeration 1.013X10 5 Pa, passivating for 3h to prepare Cu 3 Al alloy nano particles, wherein the alloy nano particle component is related to the initial alloy block component, the number of tungsten sheets placed in the alloy material, the heating temperature, atmosphere and the like.
Example 3:
(1) placing 5 tungsten sheets with phi 4mm and 1.5mm height in the middle of an alloy block (such as CuAl) cake phi 41mm and 16mm height to be evaporated on a water-cooled anode, and taking a water-cooled and ventilated cathode tungsten rod phi 6mm and 125mm length as a cathode head; the circulating water and the power supply are turned on, and the vapor deposition chamber 8 and the sealing chamber 9 are vacuumized to be 2 multiplied by 10 by using a mechanical pump and a molecular pump unit -1 Pa. Filling argon into the vapor deposition chamber 8 and the sealing chamber 9, cleaning for 2-3 times, and vacuumizing to 2×10 -3 An environment of Pa;
(2) filling hydrogen-argon mixed gas with total pressure of 9.5×10 4 Pa, wherein the pressure ratio of argon to hydrogen is P Ar :P H2 ＝4:1；
(3) Starting a controllable Wen Zhuzhuang heater, adjusting the temperature to 1000 ℃, starting a circulating pump, and adjusting the cathode ventilation amount to 40sccm;
(4) turning on an arc power supply, starting an arc with small current, and enabling the arc current to be 200A, the voltage to be 35V and the arc striking time to be 4 hours after the arc is started and stabilized;
(5) after stopping the arc, use 2X 10 4 Pa air and 8X 10 4 The mixed gas of Pa argon is circularly passivated for 3 hours, and after stopping for 1 hour, the mixed gas is pumped to 6 multiplied by 10 4 Pa, according to the air argon ratio 1: 5-cycle inflation 1.013X10 5 Pa, passivating for 4h to prepare Cu 3 Al alloy nano particles, wherein the alloy nano particle component is related to the initial alloy block component, the number of tungsten sheets placed in the alloy material, the heating temperature, atmosphere and the like.
The above experiments show that: cu prepared by the preparation method 3 Al alloy nanoparticle formationThe components are single solid solution, the particle components are related to the initial alloy block components, the number of tungsten flakes put in the alloy material, the heating temperature, the atmosphere and the like, and Cu 3 The Al nano particles have a diameter distribution of 40-90 nm and an average particle diameter of about 69nm.
Obtaining example 2, wherein the diameter phi of a CuAl cake to be evaporated is 40mm, the height is 15mm, 5 tungsten sheets with phi of 3mm and the height of 1mm are placed in the middle, and the diameter phi of a tungsten rod is 5mm and the length is 120mm; the purity of the argon used is 99.99%; the purity of the hydrogen is 99.99 percent, which has the best effect in the scheme.
FIG. 5 (a) is a TEM of a nanoparticle coated with an oxide film about 3.5nm thick, having a diameter of 62 nm; FIG. 5 (b) is an X-ray diffraction spectrum, the peak of the spectrum corresponding to alloy Cu 3 Al and a few Cu peaks.
The temperature gradient generated by the electric arc in the method is large, crystallization nuclei with special forms and structures are easy to generate, and alloy nano particles are formed by adding a high-temperature region, so that a good sample preparation method is provided for mechanism research. The method solves the problem that the content of the alloy nano particles prepared by the traditional arc method for preparing the alloy nano particles is low, is simple and reasonable, has obvious effect, and is suitable for popularization and application in the field of preparing other alloy nano particles.
Claims (6)
1. An apparatus for preparing alloy nano-particles by arc method, which is characterized in that:
the upper part of the equipment is a vapor deposition chamber (8), the vapor deposition chamber (8) is connected with a sealing chamber (9), a heater (10) with variable length and controllable temperature is arranged in the vapor deposition chamber (8), the vapor deposition chamber (8) is connected with a water-cooled anode (6) and a water-cooled ventilation cathode (7), and the lower part of the vapor deposition chamber (8) is inserted into the trapping chamber through a conical trapping tank (13);
a central channel (15) is arranged in the middle of the longitudinal direction of the heater (10), a heating part (16) is arranged around the central channel (15), a telescopic structure is arranged in the middle of the heater (10), a heat-shielding tungsten plate (17) is arranged at the bottom of the heater (10), and the heater (10) is connected with a heating power supply (12);
the axial inside of negative pole (7) is equipped with logical water route (26), and the axial outside of negative pole (7) is equipped with ventilation way (25), and the head of negative pole (7) is equipped with copper nut and is used for fixed negative pole head tungsten stick (24).
2. The apparatus for preparing alloy nanoparticles by the arc process according to claim 1, wherein:
the vapor deposition chamber (8) is connected with the molecular pump (4) through the valve (5), the molecular pump (4) is connected with the mechanical pump (3), the mechanical pump (3) and the molecular pump (4) are both connected with the power supply (1) and the control cabinet (2), and the heater (10) is connected with the heating power supply (12).
3. The apparatus for preparing alloy nanoparticles by the arc process according to claim 1, wherein:
one end of the sealing chamber (9) is provided with a heat shielding plate (19), the sealing chamber (9) is connected with the vapor deposition chamber (8) through a vapor deposition chamber wall (18), gloves, tools and raw materials (20) are arranged in the sealing chamber (9), the other end of the sealing chamber (9) is provided with a flange (21), the sealing chamber (9) is led out from inside to outside and passes through air channels (23) communicated with two sides of the gloves, and the air channels (23) communicated with two sides of the gloves are closed and opened through the air channel flange (22).
4. A method of making an alloy nanoparticle apparatus using the arc process of claim 1, characterized by: the method comprises the following steps:
(1) cutting an alloy cake to be evaporated, namely CuAl, into two blocks in the middle vertical height direction, putting proper tungsten sheets in the middle to prepare a sandwich type, putting the sandwich type on a water-cooled anode (6), and taking a tungsten rod of a water-cooled ventilation cathode (7) as a cathode head; the circulating water and the power supply are turned on, and the vapor deposition chamber (8) and the sealing chamber (9) are vacuumized to be 2 multiplied by 10 by using a mechanical pump (3) and a molecular pump (4) unit -1 An environment of Pa; filling argon into the vapor deposition chamber (8) and the sealing chamber (9), cleaning for 2-3 times, and vacuumizing to 2×10 -3 Pa ringAn environment;
(2) filling argon and hydrogen mixed gas with pressure ratio ofP Ar :P H2 =5:1～1:1；
(3) Starting a controllable Wen Zhuzhuang heater (10) power supply, adjusting the temperature to 20-1200 ℃, starting a water pump and an air pump valve of a control cabinet, adjusting the ventilation quantity of the water-cooling ventilation cathode (7) to 20-40 sccm, and enabling air flow to be used for protecting a cathode head tungsten rod (24) and controlling arc;
(4) opening an arc power supply (1), starting an arc with small current, and after the arc is started and regulated, enabling the arc current to be 150-200A, enabling the voltage to be 30-35V, and enabling the arc striking time to be 1-4 h;
(5) after stopping the arc, using 1-2X 10 4 Pa air and 9 to 8 multiplied by 10 4 The mixed gas of Pa argon is circularly passivated for 1 to 3 hours, and is pumped to 5 multiplied by 10 after stopping for 1 hour 4 Pa, according to the air argon ratio 1:5 to 1:3 aerating, and recycling passivation for 1-3 h to prepare Cu 3 Al alloy nanoparticles, the alloy nanoparticle composition is related to the starting alloy block composition, tungsten plate size, melting point of the respective elements, saturated vapor pressure, heating temperature, and atmosphere.
5. The method for preparing alloy nano-particles according to claim 4, wherein the method comprises the steps of:
the diameter phi of the CuAl cake to be evaporated is 39-41mm, the height is 14-16mm, the diameter phi of the pure tungsten sheet is 2-5mm, the height is 1-2mm, the diameter phi of the tungsten rod is 4-6mm, and the length is 115-125mm; the purity of the argon is 99.99 percent; the purity of the hydrogen was 99.99%.
6. The method for preparing alloy nano-particles according to claim 4, wherein the method comprises the steps of: prepared Cu 3 The Al nano-particle component is a single solid solution, the alloy particle component and content are related to the starting alloy block component, the tungsten plate size, the melting point of each element, the saturated vapor pressure, the heating temperature and atmosphere, cu 3 The diameter distribution of the Al nano particles is 40-90 nm, and the average particle diameter is 69nm.
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